Azo dyestuffs



Patented Feb. 27, 1940 PATENT. OFFICE AZO DYESTUFFS RichardFleischhauer and Adolf Miiller, Frankfort-on-the-Main-Fechenheim,

Germany, as-

signors to General Aniline & Film Corporation, a corporation of Delaware No Drawing; Application June 8, 1939, Serial No.

. 4 Claims.

The present invention relates to azo dyestufis,

more particularly to those of the general for-,

mula:

wherein one X stands for a sulfonic acid group and the other X stands for hydrogen, R stands for a member selected from the group consisting of aromatic radicles of the benzene and naphthalene series, Y stands for. a member selected from the group consisting of hydrogen and --N=N--R, and aryl means a radicle of the henzene series.

The new dyestuiis are obtained by combining in an alkaline medium diazo compoun'dsof aromatic amines of the benzene or naphthalene series with l-arylamino-7-hydroxynaphthalenemono-sulfonic acids or with'substitution products thereof containing in the 2-position of the naphthalene nucleus the radicle of a diazo compound of the benzene or naphthalene series.

The dyeings obtained on wool and silk by means of the present new dyestuffs are distinguished by mostly deep olive-green to brown toblack shades of generally very good fastness properties, especially of good fastness to light. It is also possible I to vary the properties of the dyestufls by asuitable selection of the diazo compounds employed for their manufacture, obtaining thereby, on the one hand, dyestufis of an especially good levelling power, and on the other hand, such of a very good fastness to fulling,v Washing, perspiration and seawater. Dyestuffs prepared by employing' o-aminopheno'lsas diazo components aresuitable for an aftertreatment with chromium compounds, on the fiber, wherebyfast olive-brown to olive-gray or olive-green shades are obtained.

Finally some :of the dyestufisprepared according to the present invention are suitable for dyeing In Germany June 9, 1938 nents for the manufacture of the present new dyestuffs have not been described, and they also have not been used for the manufacture of any other azo dyestufis. They may be prepared according to several known methods, for instance, by heating 1-amino-7-hydroxynaphtha1ene-3- or -4-sulfonic acids together with aromatic amines in the presence of salts of these amines, whereby the amino group is arylated, or by acting with sulfonating' agents on l-arylamino-l-hydroxynaphthalen'es. The l-armylamino -'7 hydroxy-r naphthalene-sulfonic acids substituted in the 2- position of the naphthalene nucleus by the radicle of a diazo compound of the benzene or naphthalene series may be'prepared by combining in an acid medium the diazo compound of an arcmatic amine of the benzene or naphthalene series with a l-arylamino-T hydroxynaphthalenesulfonic acid.

In order to further illustrate ourinvention the following examples are given, the parts being by weight. We wish it, however, to be understood that our-invention is not limited to the particular products or reaction conditions mentioned therein.

Example 1 t 173 parts of l-aminobenzene-Z-sulfonic acid are. diazotized in the usual manner and the diazo solution obtained is allowed to run into an aqueous solution of 34.5 parts of l-'(4'-methoxyphen-, ylamino)-7-hydroxynaphthalene4=-sulfonic acid containing an excess of sodium carbonate. When the combination is complete, the dyestuff formed of the formula some II N Nil-Q OH OiNa is separated and dried. It is a black powder, soluble in concentrated sulfuric acid with an orange-red and in water with a red-brown color,

and dyes wool deep brown shades of good fastness properties, especially of a very good fastness to light.

By employing the corresponding amount of 4- nitro-1-aminobenzene-2-su1fonic acid as .diazo component, a dyestuff is obtained which dyes wool deep dark-green shades.

Example 2 26.5 parts of 2-aminodiphenylether-4-sulfonic acid are diazotized in the usual manner and the diazo solution obtained is allowed to run into an aqueous solution of 31.5 parts of l-phenylamino- 7-hydroxynaphthalene-4-sulfonic acid containing an excess of sodium carbonate. The mixture is stirred until the combination is complete. The the dyestufi formed of the formula N NE 0 iNa is separated and dried. It is a black powder, soluble in concentrated sulfuric acid with a bluish-red and in water with a red-brown color, and dyes wool and silk dark-brown shades of good fastness properties especially of a good fastness to light.

The analogous dyestufi obtained with I-phenylamino-7-hydroxynaphthalene-3-sulfonic acid as coupling component yields dyeings of somewhat deeper dark-brown shades of equally good fastness properties.

Very similar dyestufis are formed by employing 4-aminodiphenylether-Zsulfonic acid as diazo component.

Example 3 The diazo solution obtained by diazotizing 17.2 parts of 1-aminobenzene-3-sulfamide is allowed to run into an aqueous solution of 31.5 parts of 1-pheny1amino-7-hydroxynaphthalene-3-sulfonic acid containing an excess of sodium carbonate. The mixture is stirred until the combination is complete. Then the dyestuff formed of the formula SO2-NH:

SOaNl.

is separated and dried. It is a. black powder, soluble in concentrated sulfuric acid with an orange-brown and in water with a red-brown color, and dyes wool dark-brown shades of goodfastness to light, fulling and perspiration. The

dyestufi has a good levelling power.

Example 4 27 parts of 1-aminobenzene-3-(N-ethyl-N- phenylsulfamide) are diazotized in the usual manner and the diazo solution obtained is combined with an aqueous solution of 31.5 parts of 1-phenylamino-7-hydroxynaphthalene-3-sulfonic acid containing an excess of sodium carbonate. The mixture is stirred until the combination is complete. Then the dyestufi formed of the formula NEG - is separated and dried. It is a. black powder, sol-.

1-(4-methy1pheny1amino) 7 hydroxynapihtha lene-4 -sulfonic, acid I 1- (2,4-dimethyl-phenylamino) -7-hydroxynaphthalene-i-sulfonic acid 1- (2' ,5'-dimethyl-phenylamino) -7 -hydroxynaphthalene-4-sulfonic acid 1 4'-hydroxy-phenylamino) 7 hydroxynaphthalene-4-sulfonic acid 1- (3' carboxy-phenylamino) -7-hydroxynaphtha- -lene-4 -sulfonic acid 1- (4-sulfo-phenylamino) 7 hydroxynaphtha-' lene-4-sulfonic acid l-(f-hydroxy- 3-carbo'xy-phenylamino) 7 '-hy-' droxynaphthaleneA-sulfonic acid whereby the shades of the dyeings andthe solubility of the dyestufis may be varied to a certain degree. v

Example 5 "I'hediazosolution obtained by diaxotining 18.9

parts of 2-amino-l-hydroxybenzene--sulfonic acid is combined with an aqueous solution of 31.5 parts 1 of I-phenylamino-7-hydroxynaphthalene- 3-sulfonic acid containing an excess of sodium carbonate. When the formation of the dyestufl" is complete the dyestuif of theformula is separated and dried. It'is a black powder, soluble in dilute ac-idswith-a red-brown, in a sodium carbonate solution-with a blue andin concentrated sulfuric acid with a bluish red color, and dyes woolgray shades turning when after- ,chromed into olive-gray shades of very good fastness to timing, potting and light.

. Example 6 17.8 parts of 4,6-dichloro -2-amino-l-hydroxybenzene are dia'zotized in the usual manner and the diazo solution obtained is allowed torun into an aqueous solution of 31.5" parts of 'l-phenylamino- '7 -hydroxynaphthalene-, 3 -sulfonic acid containing an excess of sodium carbonate. The

mixture is stirred untilthe combination is complete. Then the dyestuff formed of the formula l ('2'-methpxy-phenylamino) '7 -hydrox-ynaph- 7 aqueous. solution of 31.5 parts'of 1-ph'e'nylarnino thalene-3-sulfonic acid, I a 1 (4.methoxyphenylamino) '7 -hydroxynaphthalene-S-sulfonic acid, 1 h (2 methybphenylamino) 7 -hydroxynaphthalene-3-sulfonic acid, I 1 (4' methyl-phenylamino) thalene-B-sulfonic acid. or the 1-(2', 4-dimethyl-phenylamino) -'7-hydroxynaphthalene-3-sulfonic acid dyestufi's are obtained which dye wool when aiterchromed olive-gray shades having the same excellent fast ness properties.

7 -lrydroxynaph- Example 7 r 15.4 parts of 4-nit'ro-2-a'min0-Ihydroxybenzene are diazotized in the usual manner and'the I diazo solution obtained is. combined 'with an' 'l h droxynaphtnalene-3-su1fonic acid-containin an excess of sodium'carbonate. When the combination is complete the dyestuif formed of the formula 1 is separatedl and dried. It is a black powder,

soluble in water with an olive-green, in dilute acids with a dirty green and in concentrated sulfuric acid with a bluish-red color. The dyestuff dyes W001 from an acid bath greenish-gray shades which by after-chroming are converted into yellowish-olive shades of excellent fastness. properties, particularly to fulling, potting, hot-pressing and light.

Example 8 V A diazo solution obtained; inthe usual manner by diazotizing 12.1 parts of 3-aminobenzaldehyde is introduced while cooling into an aqueous solution of 31.5 parts of 1-phenylamino-7-hydroxynaphthalene-3-sulfonic acid. containing an excess of sodium carbonate. The mixture is stirred until the combination is complete. Then the dyestufi formed of theformula' SOaNa EEO- is separated and dried. I It is a black powder which dissolves in water with a dark brown, and in concentrated sulfuric acid with an orange-red color. It dyes Wool from an acetic acid containing' or neutral bath dark brown shades of excellent fastness properties, especially to perspiration, sea-water; fulling and light. ,The dyestuff is-also distinguished by a good levelling power.

' Example 9 A diazosolution prepared inthe usual. manner from 18.6 parts of 4-amino-l-methylbenzene-2- sulfamide is combined while cooling with an aqueous solution of 31.5 parts of l-pheriylamino- 7-liydroxynaphthalene 3 -sulfonic acid containing an excess of sodium carbonate. When the combination is complete the dyestuff formed of the formula SOaNa is separated and driedln It is a black powder,

soluble in water with a dark brown and in concentrated sulfuric acid with a red color. It dyes wool from an acid or neutral bath deep darkbrown shades distinguished by good fastness properties, especially by a good fastness to light.

A similar dyestufi is .obtainedby employing instead of the 4-amino-1-methylbenzene-2-sulfamide the l-amino-1-methylbenzene-2-sulfomethylamide. Example 10 mixture is stirred until the combination is complete. Then the dyestuff formed of the formula some is isolated. It is. when dry a black powder, soluble in Water with a dark brown and in concentrated sulfuric acid with a red color. It dyes wool from an acid or neutral bath dark brown shades of excellent fastness properties, especially to fulling, perspiration, potting, and a good fastness to light.

By employing instead of 4- (benzoyl-cyclohexylanimo) -1,-aminobenzene the 4-(benzoyl-n-butylamino) 1 aminobenzene, the 4 -(caprinyl-n'- butylamino) -1-aminobenzene, the 4-(propionylcyclohexylamino) -1-aminobenzene or the 4- (235' dichlorobenzoyl cyclohexylamino) 1 aminobenzene, dyestuffs are obtained dyeing wool dark brown shades of similar good fastness properties.

Example 11 22.3 parts of 1-aminonaphthalene-4-sulfonic acid. are diazotized in the usual manner and the diazo solution obtained is allowed to run into an aqueous solution of 31.5 parts of l-phenylamino- 7hydroxynaphthalene-3-sulfonic acid contain-' ing an excess of sodium carbonate. The mixture. is stirred until the combination is complete. Then the dyestufl formed of the formula SOaNa is separated and dried..- It is a dark powder, soluble in water, with a -gray, in.-concentrated sulfuric acid with a violet color. It dyes wool from an acid bath fast gray to black shades.

Example 12 I,

17.2 parts of l-aminobenzene l-sulfamide are diazotized in the usual manner. The acid diazo solution obtained is combined with a neutral solution of 33.8 parts of theso'dium salt of the 1-phenylamino-7-hydroxynaphthalene-3-sulfonic acid, while stirring until the combination is complete. The monoazo dyestuff thus obtained is isolated andv dissolved'in water in the presence of an excess, of sodium carbonate. tion the ;.diazo solution is introduced which is.

obtained in the usual manner-by diazotizing 29$ parts of 1.-amino-4-(benzoylethylamino)e ben zene. When .the combination. is complete the disazodyestufi formed of the formula CIIIHII I I SOzNB is separated and dried. It is soluble in water with a brown and in concentrated sulfuric acid with a bluish red color and dyes wool from an acid bath full neutral brown shades, having very; good fastness properties, especially to fulling and perspiration, and a good fastness to light.

Similar dyestuffs are obtained .by ,employing 45 instead of the 1-ph enylamino 7-hydroxynaph thalene-3-sulfonic acid derivatives thereof which are substituted in the benzene nucleus as, for instance, I I

1 -(2'- methoxyphenylamino) '7 hydroxs'maph 3 thalene-3-su lfonic acid, 1 (4- methoxyphenylamino) 7 hydroxynaph thalene-3-sulfonic acid,

1- (2-methylphenylamino) 7- hydroxynaphthalene-S-sulfonic acid,

l- GIN-methylphenylamino) 7 hydroxynaphtha-l hydroxynaph with 31.5 parts of 1-phenylamino-7-hydroxy-.

naphthalene-l-sulfonic acid. When the combination is complete the monoazodyestufi formed is separated and dissolved in water containing an excess of sodium carbonate. Into this solu'i tion the diazo' solution is introducedzobtainedi' by diazotizing 2'4 parts .of 1-amin0-4-(benzoyl-f Into this -s.0lu-,

ethylamino) -benzene. The v disazo dyestufl! formed of the formula S OaNa is separated and dried. It a dark powder, soluble in water with a brownand in concentrated sulfuric acid with aclaret red color. It-dyes wool from an acetic acid containing bath brown shades of very good fastness properties, especially to fulling, washing and perspiration, and.

of good fastne'ss to light.

By employing instead of the 1- phenyla1'nino-7 hydroxynaphthalene 4-sulfonic acid the 1- (2'-methylphenylamino) '7 hydroxynaphthalene-4-sulfonic acid, v 1- (4-methy1phenylamino) '7 a hydrjoxynaphthalene-i-sulfonic acid, I

1- (2 ',4'- dimpthylphenylamino) -7-hydroxynaph-i thalene-4-s11lfonic acid 1- (2- clrlorophenylamino) 7 hydroxynaphthalene-4-sulfonic acid I dyestuffs, are obtaineddyeing wool similar shades of equally good fastness properties.

Example 14 y A diazo solution obtained in the usual man ner by diazotizing 13.5 parts of 1-amino-3-ace-' tylaminobenzene is allowed to run into a neu-' phenylamino '7 hydroxynaphthalene 3 sulfonic acid While stirring until the combination-is com plete. The monoazodyestuff obtained is isolated parts of 4-methyl- 6-nitro z-amino-l-hydroxybenzene." Then the mixture is stirred until the f Ihe disazo dyestufl combination is complete. formed of the formula is isolated and dried. 5-11; is a dark powder, soluble in a sodium carbon'atesolution with a green-.

ish-brown, in dilute mineral acid solution with p a red-brown and in concentratedsulfuric acid with a claret-red color. It dyes wool olive-green "shades which when afterchromed are converted into olive-brownshades of very good fastness properties, especially to fulling and light.

' Example 15 22.3 parts of 1 -aminonaphthaleneal-sulfonic acid are diazotized and the diazo solution obtained is combined in the presence of an. excess of sodium carbonate with a solution of {17.6 parts of the monoazo dyestufi, which isobtained by combining diazotized 1- amino-3-acetylaminobenze'ne with 1-phenylamino-7 hydroxynaphthalene- 3-sulfonic acid in an acid medium. When the combination is complete the disazo dyestuif formed of the formula solna SO3Na Nn -ooona is separated and dried. It is 'a darkpowder,

- soluble in water with a brown and'in concentrated sulfuric acid with a violet color. It dyes wool fast brown shades.

Emdmple 16 22.3 parts of 1-aminonaphthalene 4-sulionic 1 acid are diazotized and the 'aciddiazo suspension is combined with a neutral solution of 31.5 parts .of l-phenylamino7-hydroxynaphthalene-3 su1- fonicacid." VVhen the combination is comp-lete the mixture is rendered weakly alkaline by the addition of a sodium carbonate solution. 'I'heformed monoazo dyestufi is precipitated I by the-addition of salt, and redissolved in waterbwith. the addition of an excess of sodium,

Then the solution obtained is altral solution of 33.8 parts of the sodium salt of "1-" lowed run slowly while stirrmg into a maze carbonate.

solution obtained by diazotizing in the'usual manner. 29.4 parts of 1-amino-4 (benzoyl-cyclohexylamino) -benzene. ,After' having stirred the mass for some time the. disa zo dyestufi formed of the formula isisolated and dried. It is abrown powder solu- Ible in,wate'r-withv a brown and in;concentrated sulfuric acid with a brownish-red color. Animal fibers are dyed in fast brown shades.

" Further dyestuffs obtainable according to'the which is a greenish black powder and dyes wool We claim: e 3. The azo dyestuff of the formula: 1. The azo dyestuffs of the general formula: OH

I l SOr-NH:

HO Y

x x HO- wherein one X stands for a sulfonic acid group and the other X stands for hydrogen, R stands sods-Ia for a member selected from the group consisting of aromatic radicles of the benzene and naphthalene series, Y stands for a member selected from the group consisting of hydrogen and which is a black powder and dyes wooldeep dark brown shades'of good fastness properties. 4. The azo dyestu'ff of the formula:

N=N-R, and aryl means a radicle of the 31% benzene series, which dyestuffs dye animal fibers G various shades of good fastness properties.

2. The azo dyestufi of the formula:

Ha H2 110 SOaNa which is a black powder and dyes wool darkbrown shades of excellent fastness properties,

especially to fulling, potting and perspiration.

RICHARD FIEISCHHAUER,

greenish-gray shades of excellent fastness properties, especially to tulling, hot-pressing, potting a d g t, 

